Process of making ammonium chloride



July 25, 1933. s. B. HEATH ET AL 1,919,943

rnocass OF MAKING AMMONIUM CHLORIDE Filed June '50, 1952 Reae'iion Tower Filler Cooler Jataraiad Mother I INVENTORS Sheldon .B. Haaih, BY Han-s A..Raimer.$'

ATTORNEY l at ented ul y SHELDON 1:. HEATH Ann HANSAL EIMER-SQO F,ivrinmlnnfivricniem; AssIeNoRsmo .THE-mowoHEMIcA coMrA vY, or mrnrsnn mrcnieen, A coRronATIon-or I The present invention relates to-proces s for making ammonlum chloride,v and 'par ti'cularlyto aprocess involving theinteracwith the equation tion of ammoniaand 'chlorinein accordance,

VSNHg+3CI 6N H Gl+N E I carrying out fthe foregoing reaction by directly combining the "two gases numerous 1 practical problems (arise. Th ammon um' chloride product m y be formed, as a: fog

or mist which; is extremely difficult 'to' "condenseor evento absorb iniwaten 'The'high ly exothermic 7 character the freaction' ne-f 1 ce'ssitates theprovision oft-adequate means't'o absorb'heat and to'p're'v'ent excessiver se of emperature It is also essential to avoid the .presence'fof an excessof chlorine, eve transiently, which lwould lead .tothe forma tion of the highly unstable nitrogen chloride;

and thereby, createa dangerous explosion hazard. a "some of the zfaforerhentioned diflioulties may be obviatedif thereaction iscar-ried out in the l qu P ilby tr du glthe ase into, a suitable aqueous medium, 'thusifaclli- .The latter compounds, i. e. and NHClg,

impart a pronouncedzyellowcolor toj thej solution 7' and toithe ammonium chloride I crysi tals subsequently separatedtherefrom which 4 necessitatesrecrystallization orderftoob- .tainia product sufliciently free fromcolorfto answer trade; requirements. I The avoidance of fluctuations inltheyrat'e', of:- flow of thfe 1 re-: action "gases; which would cause the intro v "duction, at leasttemporarily',-of anex'cessof either "chlorine? or ammonia, imposes a re; quirementvwhich is extremely difficultiof attainment on a large scaleg; Nevertheless, the successful;application of thereactlon n question to a commercialmanufacturing process 1932. Serial- 620,204 v extreme-accuracy in controlling-the supplies Y of ammonia and fchlorinemay beavoidedif Y the reaction is carried out'in' liquidjphase at demands a practical'solution for the last men; tioned" ifliculty, as Well'asthose preyiously referredto.

We have now found that the necessity .for a a temperature above G; By so doing the formation, of nitrogen chloride or chloram- 'i'nes is prevented', regardless of the presencejof an appreciableexcess; of chlorine or ammoniain' the reaction mixture. ,As a liq uidl medium in'WhlCh to carry out the reaction an' ammoniuni"chloride solution is most advantageous, nasmuch as-themother liquor from which the crystalsl'of thep'roduct have been, separated may be recycled to furnish ess;

and related ends, the invention, then, consists in the steps hereinafter fully described and the aqueous medium for continuing the procparticularly pointed out. in the claims, the V annexed drawing and following description i i j s'ett 1 1 1g -fo 1" th a preferred embodiment ofithe I invention whichillustrateshowever, but one i oi the invention may, be, employed. 5 .1 In said annexed'drawingf of the various ways in Whicnthe. vprinciple The "single figure-represents diag rammae iic'ally anyarrangement of apparatus suitable for carrying out-the invention," a'swell as the v v movement of materials in the-process;

, By introducing chlorine and ammoniainto a an aqueous mediumfconsistingof anammonium chloride 9 solution in which the reaction: '7

is caused to; take place, the heat evo ve sufffices t maintain the. mixture at a suitable elevated,temperature above 95 0., at the same [time permitting an e'flectiye tempera:- turej j control, due :to the heat-absorptive .ca- 7 pa'cityof Ithesol'ution, fto prevent an excessive rise l ;in temperature, 7-; The temperature 95" and Ql1 5." .QC'., ,jthe latterfbeingfthe boiling point of a saturated ammonium chloride so-- lutioni When :the 01atiqab eo 'es saturated withthe product at'thei-orea'ctiontempera maintained forthe-reaction maybe between 55 ture, it may be removed and cooled tol a lower temperature to crystallize ammonium chlobeing separated from the mother liquorand the latter being returned to the process.

The operation of our improved-process may be explained in greater detail by referenceto the drawing; An ammonium. chloride solution from a supply tank 1 is'pafssed through a heater 2, in which the temperature of the solution is raised to 95 Cher the lower part of the tower ammonia gas and chlorine are introduced, whichare absorbed or dissolved in the solutionQWhile' simultaneously reaction "oecurs'with formation of ammonium chloride. The proportions of ammonia and chlorine should be heldas closely as practicableto the theoretical pro; portions according} to the above equation. The temperature-in thereaction zoneisjtobe maintained above 95C. to prevent the formation of nitrogenchloride, or chlorainines,

if by chance excess of chlorine or v monia shouldfb'e present at any tirr1e.- In fvjides .a highly satisfactory method of em practice, the temperature at the top tof the'jploying chlorine for the reaction without the 1 tower is maintained at9 6l C. or slightly: i higher, whereas, 3 due to the reaction heat evolved, the temperature of the strong solution at the bottom at thetower may be about 100? to 105 C. under usualoperating conditions. Forthe control of the addition.

? of chlorine and ammonia an electrometric method is mostconvenient, whereby ari'indi solutionisprovidedand a control in accord ance therewith may be devised employing well-known methods}; The hydrogen ion liquor from supply tank 1 to tower 3 is preferably regulated, relative to therate of in- I troductio'n of chlorine andlam nonia, so that" the solution reaching the base of tower 3 is v nearly orapproximatelyj'saturated with arn-i monium chloride, the height' of the tower be-w in'g suficient to insure completeness of reaction andabsence of amaterial quantity of 311111101118, or cl'ilorine n the exit gases. The

lower temperature, e. a temperature :be-

x p o a. I. out vuse of artificial I'GTITIDGI'HIIIOIL Such Hdewhmh compnses absorbmg man aquer cooling is accompaniedl by precipitation of ammonium chloride crystals, forming a slurry ofcrystals and motherliquor thereof.

The crystal slurry is then filtered on a filter tank'l for reuse in the process.

The exit gases escaping from the top of tower 3,; which consist chiefly of nitrogen and inert diluent gases, e. g. air, accompanygingthe, suppl es of chlorine and ammonia gas, together with water Vapor and some ammonium chloride vapors,-as well as at times a some ammonia or chlorine, are conducted to above, and introduced into the'top' of an ab sorber tower 8, provided witha body-of pack ing material 4;, wherein the solu'tionflow's downwardly in a distributed manner. In

pounds therefrom, and then vented-from the systems The scrubberliquor is recycled con;

tiIiHOuSly untilasufiiciently strong solution is formed, and may then be introduced into the mainreactioneycle by conducting to supply tanl; 1 or to top of tower The water V a introduced in this way serves to make up evaporation losses or mechanical losses occurring iinthe nilainreaction cycle so as to maintain approxiinatelyv a constant volume of solution in'the cycle.

rThe; foregoing described process is preferable-to that involving the reaction of ammonia andhydrochloric acid in that it prointermediateconversion of the same to hythqllghla Q k 'LQ ay be used less advang H l s y eto SOInewhat, greater heat ,re-

quireinent to maintain the'desired reaction temperature, Theainmonia chloride prod not obtained directly consists of substantially cation of hydrogen ion concentrationflof the pure. and White crystals which answer the .testsxfora O. P. material, ifthea'pparatus employed is made ofinaterials resistant-to chemical ,attack, such asl glass}stoneware,

ada tor brick, carbon, etc. For pipes, pumps, etcQ one of the high-chromium cor- I s .rosion-resistantsteels is satisfactory,.not be- The rate" oi flow of ammonium chloride ing appreciably attacked under the conditions maintained aslhereinbefore' described.

Other modes of applying the principle of steps be, employed.

distinctly claim as our invention l perature between 95 and r1159 0.

2. Theprocess of making ammonium chloous ammoniuml' chloride solution ammonia and chlorine n amount corresponding to the a a o a Wetherefore particularly point out and strong hot effluent solution from; tower 3. is I conducted to, a cooler 5 of anysuitable type wherein the solution is cooled to a materially,

= ride which comprises absorbing in an aqueous ammonium' chloride solutionammonia While mistintai nin'gtithe temperature of the mixture between 95 and 115 C.

3. The process of making ammonium ch10.-

and chlorine in amount/corresponding to the equation; p

while maintaining the solution at a temperztture between 95" C. and the atmospheric boil ingpoint thereof, coolingjthe' hot solution to crystallize ammonium chloride, separate liq uor to the first step.

41' The process of inc the crvs'tals". and returning the mother ride which comprises introducing ammonia and 115 and chlorine into an aqueous ammonium chloride solution at a temperature -between 95 0., while maintaining 2r hydrogen making ammonium ch16 ion concntration'of the solution co-rresponding closely to pH =7.

5; The processof making ammonium chlomanner-f through a'scr'ubher tower an aque-' o-us ammonium chloride solution heated to a ride which comprises flowing in distributed temperature above 9 C introducing chlo- I corresponding to theequation ;sNH3+sc12+ 6 H4c1+N2;

' rine and ammonia, 'thereinto in proportions V regulating [the rate 10f introduction of uni- -mo-niaiand chlorinerelativeto the flowof solution to produce a nearly saturated solu:

tionatthentemperature existing,- cooling thev 7 hot'solut-ion to' crystallize I ammonium chiol ride, separating thelcrystals and returning the mother liquor tothe reaction.

I SHELDON B.-HEATH;

- HANSA. REIMERS." v v I fearum I 

